Separation and purification of gaseous mixtures



G. A.: BRAGG Aug. l, 1933.

SEPARATION AND PURIFICATVION OF GASEOUS MIXTURES Filed sept. 9. 1931 Ill LUSSO .owl

. kabel Ry m@ E m y WQ Patented Aug. l, v1933 UNITED STATES IPATENT OFFICE SEPARATION AD PURIFICATON OF GASVEOUS MIXTURES Gilbert A. Bragg, Pittsburgh, ra., assigiwr to The Koppers Company of Delaware, a Corporation of Delaware This invention relates to the separation of gaseous mixtures, such, for example, as coal gas, oil gas, water gas, natural gas, or the like, and other gases, such as air and gases of combustion,

from acidic constituents, such as hydrogen sulphide, carbon dioxide and hydrogen cyanide, and to the purification of gases or gaseous mixtures containing such constituents as impurities.

My invention has for an object the provision of a separation or purification process of the character set forth in which regeneration or actication of a liquid employed as absorbent for the constituents or impurities is accomplished primarily by heating the same, which process is possessed of especial advantage with respect to this method of actiflcation and in which favorable efllciencies both as to absorption and actiilcation are obtained.

My invention has for further objects such other operative advantages and results as may be found to obtain in the process or vprocesses hereinafter described.

I have found that, in certain instances, the use of heat for actiflcation possesses considerable utility, as compared with aeration or other cold actiflcation methods. vBy hot actication is meant actiflcation in which the removal of absorbed constituents or impurities is accomplished primarily by heating the solution.

Thus, while it is not true that gas separation and purification processes employing hot actication methods are always or even generally to be preferred to processes employing other types of actification, such as aeration, it is nevertheless true that there may be instances, especially when the gas to be treated or purified containsA unusually largeamounts of hydrogen sulphide, carbon dioxide or hydrogen cyanide, in which a process involving the use of hot actication may be preferred.

I have found that an aqueous solution containing an alkali metal hydroxide and boric acid or their equivalents or reaction products in a definite ratio to be described hereinbelow, has 45 especial advantages for use as the absorption medium in a gas separation or purification process in which the actication of the solution is accomplished by heating the same.

When such a solution is employed for scrubbing gases containing hydrogen sulphide, carbon dioxide, or hydrogen cyanide, the latter are absorbedfrom the gas into the solution by reaction with the alkali metal hydroxide or equivalent active alkali metal compounds contained in the solution. When the solution containing the absorbed constituent or impurity, constituents or impurities, is then heated to drive off the same and to regenerate the active absorbent constituents of the solution, the presence of the nonvolatile boric acid or its reaction or decomposition products is found to greatly facilitate the liberation of HzS, CO2 or HCN, so that substantially complete elimination of the same from the solution may be accomplished simply by boiling the solution, especially with steam.

The presence of the boric acid in the solution, however, tends to reduce the capacity of the alkali metal hydroxide or other active alkali metal compound to absorb hydrogen sulphide or the like, and it is therefore necessary to secure a balanced condition in the solution which will insure that both satisfactory absorption and satisfactory actication are obtained.

I have found that such a balance is secured and satisfactory absorption and actiflcation efllciencies are simultaneously obtained if the alkali metal hydroxide and boric acid are maintained in the solution in a molar ratio of from 0.75 1 1 to 0.40 1. A

It will be understood by those skilled in the art and by chemists generally that while the solution may be originally prepared by adding alkali metal hydroxide and boric acid as such to the solution in the stated ratio, subsequent reaction may reduce or even eliminate the ac-` tual amount of alkali metal hydroxide as such and boric acid as such which are present in the solution, and that upon contact with the gas and continued use for purification other reaction products are formed, resulting inA still further changes in the actual amounts of alkali metal hydroxide as such and boric acid as such which are present inthe solution.

Thus, it may be presumed that potassium hy droxide and boric acid react with each other to form a potassium borate or borates, and it is known that the absorption of CO2 and H2S from the gas will result in the formation of'such appreciably alkaline substances as KzS, KHS, KzCOs, KHCOs, and the like, as Well as such inert and non-alkaline substances as mSzOs, which may be formed in slight amounts. 1f HCN is absorbed, small amounts of KCNS may also be formed; this product is also inert and non-alkaline. A

.These inert materials, KnSzOa and KCNS, are not available for the absorption of HzS, CO2 or HCN and cannot beregenerated in the normal course of the process.

such inert substances as' KzSzOa or KCNS has no vbearing upon the ratio indicated above, which concerns only the alkali metal present in the form -of active, or appreciably alkaline, comvboron present as free boric acid or in combination with a portion or all of said alkali metal, calculated as HaBOa.

No diiiiculty is involvedfin determining this ratio by reason of the fact that the usual methods of determining the presence in the solution of such substances as those indicated ordinarily involve their calculation on the basis'of potassium hydroxide and boric acid, respectively.

By way of illustrative example, and for the purpose of explaining in still further detail the ratio recited above, the following method of analysis of a typical solution used for gas purication, may be of value.

A suitable portion of the solution is first titrated` with mineral acid, such as H2SO4 or HC1, of standard strength, using methyl orange as indicator. Where necessary, the indicator. is used on a spot plate. The potassium present in the solution in= the form of a compound or compounds having an alkaline reaction is then calculated (as ROH, 'when R. represents alkali metal) by standard procedure from the amount of. acid required to reach an end point.

'I'he justneutralized solution is then boiled 'to drive off substantially all volatile acidic gases (002; Has, HCN),

To the boiled solution, which then contains,.

for example, R2SO4, R2S2O3,.RCNS and free boric acid, is added mannite (mannitol, manitol) or glycerine, with phenolphthaline as indicator. The solution is'then' titrated to a lpermanent pink color after well known procedure, with CO2-free NaOH. (KOH may be used, but it is more diilicult t'o obtain in a CO2 free state.) From the amount of NaOH required', -the boric acid is calculated (as HsBOs) by standard procedure.

Such inert materials as Kas-20a, -KCNS, NazSzOa and NaCNS may be formed to a limited extent by reason of certain side reactions -i taking place in the system, but at least so far as KzSzOa and Na2S203 is concerned it has been found that the formation of these is reduced toa minimum, especially where no air or oxygen is present in the system, and probably due also in part to the beneficial eifect of the boric acid or borate in vdepressing or inhibiting the thiosulphate reaction. 'Ihe formation of KCNS and When sodium is 'employed as alkali metal,Av

the lower solubility of sodium compounds, such as sodium borates, may necessitate the use of somewhat less concentrated solutions, for example, of 3% total alkalinity, calculated as It will be obvious that the more concentrated the solution, the greater will be its carryingpower for hydrogen sulphide and other impurities, so that'the more concentrated the solution the smaller the volume of solution required per unit of gas purified. Moreover, the heating and cooling of the solution constitutes the principal operating cost of the process, and for this reason also it is desirable to use as' small an amount of solution-as possible.'

I have refrained from advancing any particular theory as to th'e reason underlying the improved actication efficiency obtainable in the lpresence of boric acid or its reaction products or as to the` precise nature of thereaction products of the boric ac id themselves, as these are matters .diilicult or incapable of actual proof and their complete understanding is not neces--l sary to the performance of my process and the obtaining of its advantageous results.-

I prefer to employ potassium compounds rather than sodium compounds by reason of the much higher solubility of the potassium borates as compared with the solubility of the sodium borates. This higher solubility enables me to employ more concentrated solutions without precipitation of the various compounds from the solution, which precipitation would of course be undesirable,

In actual practice some losses Vof reactive materials will be encountered bothby reason of mechanical losses and by reason of such formation of inertr products of side reactions" as may occur. Consequently, during the continuance ofthe process it is from time 'to time necessary to add fresh quantities of alkali metal hydroxide and boric acid or their equivalents to the solution.

However, so far as is known, the side reactions do not affect the boric acid or borates. Itis necessary to add boric acid in very much smaller quantity than alkali metal hydroxide. Consequently, while in preparing the solution the molar ratio indicated above should be adhered to, ity will be obvious that during the continuance of the process alkali metal hydroxide and boric acid may not be added in this ratio but are added in such amounts as to maintain in the solution the desired concentration andv ratio, as recited above.

The process is carried out in a cycle comprising principally an absorption stage and an actiilcation stage, and for best operating efllciency -the recirculation of the solution through this cycle is continuous. y The reactions ltaking place in the absorption stage are facilitated by increased pressure' and a low temperature, whereas the reactions taking place in the actier are accomplished, as in dicated above, at a high temperature and preferably ata reduced pressure. In general, it is ordinarily desired to accomplish actiflcation at a. pressure somewhere between atmospheric pressure and a vacuum of 20" of mercury.

In order that my invention may be clearly exemplied, I now describe, with reference to las the accompanying drawing, a preferred manner lThe single iigureis a more or less-diagrama conduit 4 to the top of the absorber 1.

matic elevational view of apparatus suitable for the purification of fuel gas by means of my process. v

Referring to the drawing, it will be seen that the principal apparatus elements are an absorber 1 and an actiiier 2. These elements are shown as conventional bell-and-tray type columns arranged for counterow of gas and liquid,

. but it will be obvious that other types of gasand-liquid-contact apparatus may be employed and that concurrent flow apparatus may be substituted for counterilow apparatus wherever desirable.

In the present instance, the gas to be purified enters the bottom of the absorber 1 through an inlet 3 and passes upward through the absorber 1 in countercurrent to the downward flow of the purifying solution which is admitted through passes downward through the absorber 1 and absorbs the bulkof the acidic impurities from the gas. Upon reaching the bottom of the absorber 1, the solution is withdrawn through a conduit 6 and delivered by a pump 7 to a heat exchanger 8 where it absorbs heat from the hot actied solution leaving the actifier 2, as

will be described hereinbelow.

The heated solution then passes through a conduit 9 having a Valve 10 and through an indirect heater 12 located in the conduit 9 to the upper portion of the actier 2. The heater 12 in the conduit 9 is provided wtih a valved inlet 13 for the admission of a heating fluid, such as steam, and may also be provided with a valved condensate drain pipe 14.

If suicient heating of the solution has been accomplished in the heat exchanger 8, all or a portion of the solution, instead of being passed through the heater 12, may be by-passed around the latter through a conduit 15 having a valve 16.

The solution containing the impurities absorbed from the gas in the absorber 1 then passes downward through the interior of the actier 2. Heat is meanwhile supplied to the solution either' through a direct steamvinlet 18- or an indirect steam coil 19, which are provided in the actiiier 2 for that purpose, or by means of any other suitable heating device or method.

Whether direct or indirect steam is used, the solution is brought to its boiling point or a little below same and maintained at such temperature until the impurities removed from the gas are in turn removed from the solution to the desired extent, that is to say, until the solution is again capable of accomplishing a suitable purication 'of the gas when returned to the absorber 1.

The hot actified solution is then withdrawn from the bottom of the actier 2 through a conduit 21 by means of a pump 22 and is delivered to the indirect heat exchanger 8, where, as above noted, it is brought into indirect contact with the fouled solution leaving the absorber 1 and gives up a considerable portion of its heat to the fouled solution. The thereby partially cooled actied solution then passes through a conduit 23 to an indirect cooler 24 of The' conduit 30 may contain considerable .amounts of steam.

Where direct steam is employed for heating the solution in the actier 2 it is not suitable to return this steam/in condensed form to the solution, butwhere indirect steam is employed for heating it may be desirable to condense and return this steam to the solution in order to prevent loss of the latter by evaporation. For this purpose the conduit 30 is provided with a condenser 31 having conduits 32 and 33 for the admission and removal, respectively, of a cooling medium such as water.

The gases passing through the? condenser 31 `are cooled to below the condensingpoint of steam and the aqueous condensate may be returned to the actifier 2 through a sealed conduit 34 having a valve 35, or, where the return of this condensate to the actier 2 is not desired, it may be drawn off through a conduit 36 having a valve 37.

When the pressures in the absorberv 1 are greater than atmospheric, a suitable pressurerelease device (not shown) may be inserted in the conduit 6 for maintaining the desired pressure in the absorber. Also, the conduit 30 may be placed in communication with a suitable exhauster or vacuum pump or other device for maintaining the reduced pressure within the actier 2.

It will be obvious to those skilled in the art that the apparatus shown in the drawing by way of illustrative example is more orV less conven-` tional and is susceptible of considerable modification in detail, arrangement and the like, and `my process is consequently not to be limited to -the use of the particular apparatus shown in the gure.

It will be apparent from the above that the process of my invention is'admirably suited for the purification of gases from acidic impurities such as hydrogen sulphide, hydrogen cyanide and carbon dioxide, especially where the use of small quantities of absorbent liquid and hot actication methods are desired. Among the advantages of my process may be included relaabsorber 1 is hydrogen sulphide, the hydrogenA sulphide liberated in the actier 2 will be especially suitable for the manufacture of sulphuric acid. As la typical example of lthe application of my process may be mentioned the purication l th from hydrogen sulphide of cracking still gases vproduced in an oil refinery, the hydrogen sulphide being converted to sulphuric acid which may subsequently be used for the refining of the oil produced in the refinery. f

The carrying power of my solution with respect to impurities is very great and the amount of solution necessary to effect a given purifying or separating operation is correspondingly low. This results in reduction of the sizes of the individual absorption and actiflcation units as well as in the size of the plant as a whole, and also in decreased costs of pumping and other incidental expenses.

Except as indicated above, the actual concentrations, rate of recirculation of the solution, temperatures and pressures are best judged by the operator in accordance with the particular purification problem dealt with in each case, and.

being matters well within the grasp of those skilled in the art need not be recited in further detail here. Consequently, it will be obvious that my invention is not limited to any operative details disclosed hereinabove except as specified in the claims hereinafter made. I

It will also be apparent, that while my invention has especial advantage with reference to the purification of gases from HzS, CO2 or HCN,

present as impurities, in its broad aspect it is not limited to gas puriiication, but may be applied to the separation of HzS, CO2 or HCN, or any combination of the same, from gaseous mixtures of Whichthey are constituents, whether principal or secondary.

I claim as my invention:

1.- The process of separating acidic gases such -as HzS, CO2 and HCN from a gaseous mixture containing them, which comprises washing the flowing gaseous mixture v vith an absorbent liquid, removing the absorbent liquid from the gas, heating it to drive orf absorbed acidic gasesand recirculating it over the owing gaseous mixture for further absorption of acidic gases, said liquid comprising a solution containing alkali metal present in a compound or compounds having an alkaline reaction, and boron present as free boric acidor in combination with a portion or all of said alkali metal, the molary ratio 'of said alkali metal to said boron being from 0.75:1 to` 0.40:1, calculated as ROH (where R represents alkali metal) and HaBOa, respectively.

2. The process of separating acidic gases such as HzS, CO2 and HCN from a gaseous mixture containing them, which compriseswashing the owing gaseous mixture with an absorbent liquid, removing the absorbent liquid from the gas,

present in a compound or compounds having 'an alkaline reaction, and boron present as free boric acid or incombination with a portion or all of said alkali metal, the molar ratio of said alkali metal to said boron being from 0.75z1 to 0.40z1, calculated as ROI-I (where R represents alkali metal) and HaBOa, respectively, and said heating of the solution taking place under a pressure less thn atmospheric.

3. The process of separating acidic gases such as HzS, CO2 and HCN from a -gaseous mixture containing them, which comprises washing the flowing gaseous mixture with an absorbent liquid, removing the absorbent'liquid from the gas, heating it to drive off absorbed acidic gases and recirculating it over the flowing gaseous mixture for further absorption of acidic gases, said liq uid comprising a solution containing potassium present in afcompound or compounds having an alkaline reaction, and boron present as free boric acid or in combination with a portion or all of said potassium, the molarj ratio of said potassium to said boron being from 0.75:1 to 0.4021, calculated as KOH and HsBOs, respectively.

4. The process of separating acidic gases such as HzS,-CO2 and HCN from a gaseous mixture containing them, which comprises washing theA flowing gaseous mixture with an absorbent liquid, removing the absorbent liquid from the gas,

heating it to drive ofi absorbed acidic gases and recirculating it over the flowing gaseous mixture for further absorption of acidic gases, said liquid comprising a solution containing potassium present in a compound or compounds having an alkaline reaction, and boron present as free boric acid or in combination with a portion or all of said potassium, the molar ratio of said potassium to said boron being from 0.75:1 to 0.4021, calculated as KOH and HaBOa, respectively; the total alkalinity of the solution, calculated as KOH, being of the order of 5% by weight'of the solution, or more.

5. The process of separating acidic gasessuch as HzS, CO2 and HCN from a gaseous mixture containing them, which'compriseswashing the flowing gaseous mixture with an absorbent liquid, removing the absorbent liquid from the gas, heating it to drive off absorbed acidic gases and recirculating it over the iiowing gaseous mixture for further absorption of acidic gases, said liquid comprising a solutioncontaining sodium present in a compound or compounds having an alkaline reaction, and boron present as free boric acid or in combination with a portion or all of said sodium, the molarratio of' sai/i sodium to saidv boron being from 035:1 to 0.40:;t, calculated `as NaOH and H3 BO3, respectively.

' GILBERT A. BRAGG. 

